In Situ Synthesis, Structure and Fluorescent Properties of Copper Metal Complexes Based on N-heterocycles Ligands
|Keywords||In situ click Copper (I) Tetrazolium Triazole Double ring Ligand conversion Fluorescence|
Heat in situ synthesis of complexes of water (solvent) is an environmentally friendly, efficient, simple synthesis methods, namely the use of high-temperature high-pressure synthesis difficult to obtain a new ligand of the traditional methods, which generate a new ligand can be reacted with a metal ion The novel features of the formation of structure complexes. This article precursor for rigidity and symmetry of the cyano-containing six-membered heterocyclic synthesis of tetrazole and triazole complexes with monovalent copper in situ study of the fluorescence properties. This thesis is divided into a total of four chapters: The first chapter introduces the research background, highlight the metal organic framework crystal engineering, design regulatory factors, the pressure is discoloration of the metal-organic complexes, identification of small organic molecules and in situ ligand conversion reaction, and also outlines the progress of tetrazole complexes in situ synthesis and in situ synthesis of triazole. Described the significance of the topic of this paper. Chapter II System the cuprous on self-assembled in situ regulation tetrazole and triazole complexes. Complexes 1, 2, 3, three complexes are two-dimensional layer in situ synthesis process, the selection of the pyrimidine nitrile ligand, sodium azide and cuprous oxide in different solvents under the action of three novel pyrimidine structure. Complexes simultaneously containing triazole and four nitrogen azole by dropping ammonia successful to achieve a double into the ring to achieve the effect of one stone two birds of; cyano, triazole tetraaza azole-based group acts as a chain rod to of Cu (I ) linked to form a layered structure. Complex 2 is a tetrazole having the structural unit of the six-membered ring with the polymer. Complex 3 is a triazole coordination environment containing four different Cu (I) complex. We can see that the ammonia and Cu (I) in the in situ self-assembled skeleton of the multi-azole complexes played a very important role in the formation process. Meanwhile, their solid-state fluorescence characteristics and thermal gravimetric the study. Only one of a phosphor, and this contains the thermal stability of the three nitrogen and tetrazole double ligand complexes to be more stable than separate complexes containing triazole or tetrazole, which is in the polyaza salt rare. The third chapter of the main work is to study the pyrimidine cyanide solvothermal in situ reaction of Cu (I) and sodium azide. By regulating solvent, wife body pyrimidine cyanide transform successful hydrolysis of the cyano decyanation and click into the ring. In this chapter, we get four complexes 4,5,6,7. Complex 4, space group with a chiral off cyano after the pyrimidine ring of the pyrimidine cyanide and cuprous iodide form Cu4I4 cluster 5 is a pyrimidine cyanide pyrimidinecarboxylic acid hydrolysis into the formation of the structure of the oligonucleotide, the free water molecules form (H2O) 4 clusters, there is a network of hydrogen bonds. 6 and 7, the cyano group to-click \6 in the pyrimidine the tetrazolium six nitrogen atoms are all involved in the coordination, this coordination mode is rarely reported, the positive divalent transition from a positive price in the formation of complexes 5 and 7 copper process, we are also complex 4 and 6, the fluorescence. Chapter IV main job is System pyridyl piperazine, Cu (I), and sodium azide in the thermal condition of the solvent, synthesis and characterization of three types of 8 complexes (8-15), wherein 8. 9,10 a two-dimensional structure is the ABAB arranged 11 AAA two-dimensional packing structure ,12-15 is a three-dimensional structure. The complexes 8 excluded the guest molecules generated after 9, both stacking mode change significantly after 9 soak solvent becomes 10 structure with 8, but different guest molecules, to achieve the conversion of the single crystal. 11 for AAA two-dimensional accumulation lead to very different (red shift of 60 nm) with 8 fluorescent precisely because of the different structure of such deposits. By polishing because of their own structural features, we can change the distance between the layers, resulting in changes in the role of the Cu ... Cu, so that the fluorescence along redshift pressure changes, namely discoloration. After dropping 8 grinding of small organic molecules solvent makes its fluorescence emission peak blue shift. 12-15 is isomorphic three-dimensional supramolecular complexes with different guest molecules and with different fluorescence properties. The presence of the guest molecules may lead to different coordination center metal cupprous ligand Cu-N bond lengths and angles, and other guest molecules and ligands pyridine tetrazolium there are weak interactions, these factors may result in them The fluorescence properties of different. We also study the recognition of small organic molecules, nitrobenzene them obvious quenching effect.